本申请旨在通过密度泛函理论、含时密度泛函理论计算与分子动力学模拟相结合来研究设计基于MAX相、MOFs和COFs以及具有非传统化学成键特征的单层和有限层的与石墨烯结构类似的二维无机材料：无机石墨烯。深入研究理解层间有较强作用力的无机层状材料在形成单层和有限层结构时的热力学稳定性，研究表面钝化、结构重组和化学修饰对其几何结构和电子结构的影响。通过计算研究并设计基于金属卟啉、酞菁等新型二维MOFs和COFs，研究其物理与化学性能以及与石墨烯复合对其性能的影响。在无机石墨烯设计中引入非传统成键方式，探讨弱相互作用在无机石墨烯和石墨烯/无机石墨烯自组装过程中对材料结构和性能的影响。通过理论计算与实验相结合探索无机石墨烯及其复合物在染料敏化太阳能电池中的应用。本研究将为设计和制备高性能光电极材料提供理论依据和实验指导。

In this proposal we aim to study and design inorganic graphenes, graphene-analagous two-dimensional (2D) single- and few-layer inorganic materials, which are based on MAX phase, metal organic frameworks (MOFs), covalent organic frameworks (COFs) and molecules with non-conventional chemical bonds, by combining density functional theory (DFT) and time-dependent DFT (TD-DFT) computations as well as molecular dynamics (MD) simulations. We will try to deeply disclose the thermodynamic stablity of single- and few-layer structures exfoliated from layered inorganic materials with strong interlayer interaction, and to investigate the effects of suface passivation, structural reconstruction, and chemical functionalization on the geometrical and electronic structures of inorganic graphenes. By computationally studying and designing 2D MOFs and COFs based on metal porphyrin and phthalocyanine, we will investigate their physical and chemical properties, as well as their property changes when forming composites with graphene. Also, the non-conventional chemical bonding will be introduced to the design of inorganic graphenes, and accordingly the effects of weak interactions will be clarified on the structures and properties of inorganic graphenes or graphene/inorganic graphene self-assemblies. Finally we will exploit the applications of inorganic graphenes and their composites in dye-sensitized solar cells (DSSCs) through the combination of computations and experiments. All the results may provide theoretical basis and experimental guidance for designing and preparing high-performance DSSC electrode materials.